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1.
Anal Chem ; 96(37): 14926-14934, 2024 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-39219294

RESUMEN

In conventional metal-organic framework (MOF) luminophore-involved electrochemiluminescence (ECL) systems, the aggregation-caused quenching commonly exists for the organic luminescent ligands, limiting the ECL efficiency and detection sensitivity. Herein, by employing the aggregation-induced emission luminogen (AIEgen) 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene (H4TCBPE) as a ligand, one high-efficiency ECL emitter (Zr-MOF) was synthesized through a simple hydrothermal reaction. Compared with H4TCBPE monomers and their aggregates, the resultant Zr-MOF possesses the strongest ECL emission, which is mainly attributed to the framework-induced ECL enhancement. Specifically, the heterostructure was prepared by the deposition of silver nanoparticles on TiO2 microflowers and utilized as an efficient coreaction accelerator. Remarkably, the formative heterojunction can increase the interfacial charge transfer efficiency and promote the carrier separation, facilitating the oxidation of coreactant tripropylamine. In this way, a novel aptamer-mediated ECL sensing platform is constructed, achieving the sensitive analysis of adenosine triphosphate with a low detection limit of 0.17 nM. As a proof-of-concept study, this work may enlighten the rational design of new-type MOF-based ECL materials and expand the application scope of the ECL technology.


Asunto(s)
Técnicas Biosensibles , Técnicas Electroquímicas , Mediciones Luminiscentes , Nanopartículas del Metal , Estructuras Metalorgánicas , Plata , Titanio , Titanio/química , Plata/química , Estructuras Metalorgánicas/química , Técnicas Biosensibles/métodos , Nanopartículas del Metal/química , Límite de Detección , Adenosina Trifosfato/análisis , Aptámeros de Nucleótidos/química , Circonio/química
2.
Anal Chem ; 96(31): 12593-12597, 2024 08 06.
Artículo en Inglés | MEDLINE | ID: mdl-39041729

RESUMEN

In this Letter, a sensitive DNA sensing platform was developed using an indium-ion-coordinated 1,1,2,2-tetra(4-carboxylphenyl)ethylene (TPE) metal-organic gel (In-MOG) as an aggregation-induced electrochemiluminescence (AIECL) emitter and nanosurface energy transfer (NSET) as an efficient quenching strategy for detecting aflatoxin B1 (AFB1), the most dangerous food toxin. The coordination occurred in indium ions, and carboxyl groups restricted the internal rotation and vibration of TPE molecules, forcing them to release photons via radiative transitions. The quenchers of microfluidic-produced gold nanoparticles were embedded in a long-tailed triangular DNA structure, where the quenching phenomenon aligned with the theory of ECL-NSET under the overlap of spectra and appropriate donor-acceptor spacing. The proposed analytical method showed a sensitive ECL response to AFB1 in the wide concentration range of 0.50-200.00 ng/mL with a limit of detection of 0.17 ng/mL. Experimental results confirmed that constraining luminescent molecules using coordination and bonding to trigger the AIECL phenomenon was a promising method to prepare signal labels for the trace detection of food toxins.


Asunto(s)
Aflatoxina B1 , Técnicas Electroquímicas , Transferencia de Energía , Mediciones Luminiscentes , Aflatoxina B1/análisis , Oro/química , Nanopartículas del Metal/química , ADN/química , Geles/química , Límite de Detección
3.
Mikrochim Acta ; 191(8): 480, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-39046571

RESUMEN

An original molecular imprinting photoelectrochemical (PEC) sensor for sarcosine detection based on stable lead-free inorganic halide double perovskite Cs2AgBiBr6 is proposed. Cs2AgBiBr6 as a lead-free halide perovskite material possesses several positive optoelectronic properties for PEC analysis, such as long-lived component to the charge-carrier lifetime, and strong absorption of visible light. At the same time, two-dimensional materials also offer excellent electronic and mechanical properties; thus, Bi2O2S was used and combined with Cs2AgBiBr6 to provide a stable and large photocurrent, which also benefits from the  stability of perovskite Cs2AgBiBr6. Based on this novel PEC assay, the detection range for sarcosine was between 0.005 and 5000 ng/mL with a low detection limit of 0.002 ng/mL. This work also improved the adhibition of metal halide perovskite in analytical chemistry field, providing a novel way for other small molecule detection.

4.
Talanta ; 277: 126346, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-38897010

RESUMEN

A novel dual-mode biosensor was constructed for the ultrasensitive detection of neuron-specific enolase (NSE), utilizing Tb-Cu MOF@Au nanozyme as the signal label to effectively quench the photoelectrochemical (PEC) signals of Bi2O3/Bi2S3/AgBiS2 composites and initiate fluorescent (FL) signals. First, Bi2O3/Bi2S3/AgBiS2 heterojunction with excellent photoelectric activity was selected as the substrate material to provide a stable photocurrent. The well-matched energy levels significantly enhanced the separation and transfer of photogenerated carriers. Second, a strategy of consuming ascorbic acid (AA) by Tb-Cu MOF@Au nanozyme was introduced to improve the sensitivity of the PEC/FL biosensor. Tb-Cu MOF@Au not only could catalyze the oxidation of AA, but the steric effect further reduced the contact of AA with the substrate. More importantly, in the presence of H2O2, a significant fluorescence was produced from Tb3+ sensitized by the oxidation products of AA. Based on the above strategies, a highly stable and sensitive dual-mode biosensor was proposed for accurate NSE determination. Third, the developed dual-mode biosensor demonstrated excellent performance in detecting NSE. In this study, the PEC method demonstrated a wide detection range from 0.00005 to 200 ng/mL with a low detection limit of 20 fg/mL. The FL method exhibited a linear range from 0.001 to 200 ng/mL with a detection limit of 0.65 pg/mL. The designed biosensor showed potential practical implications in the accurate detection of disease markers.


Asunto(s)
Técnicas Biosensibles , Bismuto , Cobre , Oro , Fosfopiruvato Hidratasa , Terbio , Técnicas Biosensibles/métodos , Bismuto/química , Oro/química , Fosfopiruvato Hidratasa/análisis , Fosfopiruvato Hidratasa/química , Fosfopiruvato Hidratasa/metabolismo , Cobre/química , Terbio/química , Humanos , Estructuras Metalorgánicas/química , Fluorescencia , Límite de Detección , Sulfuros/química , Técnicas Electroquímicas/métodos , Nanopartículas del Metal/química , Plata/química
5.
Anal Chem ; 96(27): 11044-11051, 2024 07 09.
Artículo en Inglés | MEDLINE | ID: mdl-38937378

RESUMEN

Metal nanoclusters (NCs) as a new kind of luminophore have acquired sufficient interest, but their widespread application is restricted on account of their relatively low electrochemiluminescence (ECL) efficiency. Then, aqueous metal NCs with high ECL efficiency were strongly anticipated, especially for the ultrasensitive analysis of biomarkers. Herein, a near-infrared (NIR) ECL biosensing strategy for the test of neuron-specific enolase (NSE) was proposed by utilizing N-acetyl-l-cysteine (NAC)- and cysteamine (Cys)-stabilized gold NCs (NAC/Cys-AuNCs) as ECL emitters with the NIR ECL emission around 860 nm and a metal-organic framework/palladium nanocubes (ZIF-67/PdNCs) hybrid as the coreaction accelerator through their admirable electrocatalytic activity. The NIR emission would reduce photochemical injury to the samples and even realize nondestructive analysis with highly strong susceptibility and suitability. Furthermore, the utilization of ZIF-67/PdNCs could improve the ECL response of NAC/Cys-AuNCs by facilitating the oxidation of the coreactant triethylamine (TEA), leading to the production of a larger quantity of reducing intermediate radical TEA•+. Consequently, NAC/Cys-AuNCs with ZIF-67/PdNCs displayed 2.7 fold enhanced ECL emission compared with the single NAC/Cys-AuNCs using TEA as the coreactant. In addition, HWRGWVC (HWR), a heptapeptide, was introduced to immobilize antibodies for the specially binding Fc fragment of the antibodies, which improved the binding efficiency and sensitivity. As a result, a "signal-on" immunosensor for NSE analysis was obtained with an extensive linear range of 0.1 to 5 ng/mL and a low limit of detection (0.033 fg/mL) (S/N = 3). This study provides a wonderful method for the development of an efficient nondestructive immunoassay.


Asunto(s)
Biomarcadores , Técnicas Electroquímicas , Oro , Mediciones Luminiscentes , Nanopartículas del Metal , Estructuras Metalorgánicas , Oro/química , Estructuras Metalorgánicas/química , Nanopartículas del Metal/química , Inmunoensayo/métodos , Técnicas Electroquímicas/métodos , Biomarcadores/análisis , Cobalto/química , Humanos , Fosfopiruvato Hidratasa/análisis , Límite de Detección , Cisteamina/química , Paladio/química , Rayos Infrarrojos , Técnicas Biosensibles/métodos
6.
Talanta ; 276: 126272, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38776780

RESUMEN

The development of photoelectrochemical (PEC) biosensors plays a critical role in enabling timely intervention and personalized treatment for cardiac injury. Herein, a novel approach is presented for the fabrication of highly sensitive PEC biosensor employing Bi2O3/MgIn2S4 heterojunction for the ultrasensitive detection of heart fatty acid binding protein (H-FABP). The Bi2O3/MgIn2S4 heterojunction, synthesized through in-situ growth of MgIn2S4 on Bi2O3 nanoplates, offers superior attributes including a larger specific surface area and more homogeneous distribution, leading to enhanced sensing sensitivity. The well-matched valence and conduction bands of Bi2O3 and MgIn2S4 effectively suppress the recombination of photogenerated carriers and facilitate electron transfer, resulting in a significantly improved photocurrent signal response. And the presence of the secondary antibody marker (ZnSnO3) introduces steric hindrance that hinders electron transfer between ascorbic acid and the photoelectrode, leading to a reduction in photocurrent signal. Additionally, the competition between the ZnSnO3 marker and the Bi2O3/MgIn2S4 heterojunction material for the excitation light source further diminishes the photocurrent signal response. After rigorous repeatability and selectivity tests, the PEC biosensor exhibited excellent performance, and the linear detection range of the biosensor was determined to be 0.05 pg/mL to 100 ng/mL with a remarkable detection limit of 0.029 pg/mL (S/N = 3).


Asunto(s)
Técnicas Biosensibles , Bismuto , Técnicas Electroquímicas , Técnicas Biosensibles/métodos , Bismuto/química , Técnicas Electroquímicas/métodos , Electrodos , Humanos , Procesos Fotoquímicos , Sulfuros/química , Límite de Detección , Proteínas de Unión a Ácidos Grasos/análisis , Indio/química , Compuestos de Zinc/química , Compuestos de Estaño/química
7.
Dalton Trans ; 53(19): 8269-8274, 2024 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-38659319

RESUMEN

The substantial expense associated with catalysts significantly hampers the progress of electrolytic water-based hydrogen production technology. There is an urgent need to find non-precious metal catalysts that are both cost-effective and highly efficient. Here, the porous Ni2P-FePx nanomaterials were successfully prepared by hydrothermal method, nickel foam as the base, iron nitrate solution as the caustic agent and iron source, and finally phosphating at low temperature. The obtained porous Ni2P-FePx nanosheets showed excellent catalytic activity under alkaline PH = 14, and an overpotential of merely 241 mV was required to achieve a current density of 50 mA cm-2. The morphology of the nanosheet can still be flawlessly presented on the screen after 50 h of working at high current density.

8.
Anal Chem ; 95(49): 18295-18302, 2023 Dec 12.
Artículo en Inglés | MEDLINE | ID: mdl-38016920

RESUMEN

The accurate discernment and separation of chiral isomers with high precision remain a significant challenge in various industries and biological fields. In this investigation, an electrochemiluminescent (ECL) chiral recognition platform was devised to ascertain the presence of phenylalanine (Phe). Notably, a homochiral [Ni2(l-asp)2(bipy)] (Ni-LAB) was established as a dual-function coreactant accelerator and chiral recognition substrate. Ni-LAB facilitates the reaction between the coreactant (K2S2O8) and the luminescent entity 3,4,9,10-perylenetetracar-boxylic-l-cysteine (PTCA-cys), thereby enhancing the ECL luminescence efficiency and improving the sensitivity of the chiral sensor. The chiral recognition potential of Ni-LAB was assessed to differentiate between Phe chiral isomers, and the underlying mechanism was comprehensively elucidated. This system exhibited remarkable proficiency in detecting Phe enantiomers and precisely differentiating a single Phe enantiomer within a mixture, showcasing exceptional levels of selectivity, stability, and reproducibility. This study paves the way for the development of advanced chiral recognition systems, potentially revolutionizing the field of chiral sensing and discrimination.

9.
Anal Chem ; 95(45): 16761-16770, 2023 Nov 14.
Artículo en Inglés | MEDLINE | ID: mdl-37905934

RESUMEN

Copper nanoclusters (Cu NCs) are highly promising nanomaterials in the field of electrochemiluminescence (ECL). Nevertheless, their limited stability and efficiency have impeded their practical applications. Here, we introduced a novel supramolecular anchoring strategy resulting in the creation of exceptionally stable Cu NCs (CET-Cu NCs) with remarkable ECL properties. Specifically, CET-Cu NCs exhibited a relative ECL efficiency (ΦECL) of 62% based on the annihilation ECL efficiency of [Ru(bpy)3]2+ (100%), with tripropylamine employed as a coreactant. Moreover, CET-Cu NCs can generate ECL emission through multiple different paths, which enables them to serve as signal probes in a wider range of testing scenarios, thereby enhancing the reliability and robustness of sensing and analytical systems. To demonstrate the practical utility, CET-Cu NCs were selected as an ECL signal probe for a sensing platform that facilitated ultrasensitive detection of progesterone via oriented immobilization technology and antibody/aptamer sandwich assays. This study surmounted the barriers to the practical application of Cu NCs through the implementation of a supramolecular anchoring strategy, thereby providing enhanced utility of Cu NCs in ECL sensing and analysis.

10.
Anal Chem ; 95(39): 14659-14664, 2023 Oct 03.
Artículo en Inglés | MEDLINE | ID: mdl-37725048

RESUMEN

The recognition and separation of chiral isomers are of great importance in both industrial and biological applications. In this study, a chiral recognition system based on electrochemiluminescence was established for the detection of penicillamine (PA) enantiomers. The system utilized a homochiral [Zn2(BDC)(d-lac)] (Zn-BL) platform for the uniform distribution of Ru(bpy)32+ nanoparticles, effectively mitigating aggregation-caused quenching. The chiral recognition ability of Zn-BL was tested to distinguish between PA enantiomers, and the results indicated a substantial increase in the chiral electrochemiluminescence (ECL) signal when l-PA was present, in contrast to d-PA. The mechanism underlying ECL chiral discrimination was investigated using water contact angle measurements, DFT calculations, and electrochemical characterization. The system exhibited high selectivity, stability, and reproducibility for PA enantiomer detection. Furthermore, the proposed method can accurately identify one enantiomer of PA in a mixture. This study provides a reliable and sensitive approach for achieving the highly selective detection of chiral molecules.

11.
Nanoscale ; 15(38): 15600-15607, 2023 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-37740308

RESUMEN

As for the hydrogen production process via electrocatalytic water splitting, the green and sustainable electro-oxidation of organic molecules at the anode is thermodynamically more favourable than the oxygen evolution reaction (OER). Here, we proposed for the first time to replace the OER process by the oxidation of N-Boc-4-piperidine methanol (BPM), via a parallel reaction, which finally leads to the green production of N-Boc-4-piperidine carboxaldehyde (BPC). The amorphous NiFeO(OH) nanospheres with rich valence states were adopted as the anode catalyst, with creation of more active sites. The gas chromatography results showed that nearly all the BPM converted to BPC after 15 h reaction. The electrochemical tests showed that the Faraday efficiency (FE) approaches nearly 100% when the charge transfer is approximately equal to the theoretical charge. This work reports a new process for the alcohol oxidation, providing a valuable green organic synthesis process.

12.
Anal Chem ; 95(16): 6655-6663, 2023 04 25.
Artículo en Inglés | MEDLINE | ID: mdl-37018483

RESUMEN

The essential expansion of electrochemiluminescence (ECL) technology into clinical detection relies on sensitive and stable signal and maintenance of the activity of the immune molecules during the analysis. This poses a critical challenge for an ECL biosensor as a luminophore in general requires high potential excitation resulting in a strong ECL signal; nevertheless, it has an irreversible effect on the activity of the antigen or antibody. Herein, a novel electrochemiluminescence (ECL) biosensor utilizing nitrogen-doped carbon quantum dots (N-CQDs) as emitters and molybdenum sulfide/ferric oxide (MoS2@Fe2O3) nanocomposites as a coreaction accelerator was developed for detection of neuron-specific enolase (NSE), a biomarker of small cell lung cancer. The doping of nitrogen allows the CQDs to exhibit ECL signals with low excitation potential, with a more viable activity possible for immune molecules. MoS2@Fe2O3 nanocomposites exhibit superior coreaction acceleration characteristics in hydrogen peroxide than any single component of them, and the highly branched dendrite microstructure provides a large number of binding sites for immune molecular, which is an inevitable factor for trace detection. In addition, ion beam sputtering gold particle technology is introduced into the sensor fabrication via an Au-N bond, which will provide sufficient density orientation for capturing the antibody load via the Au-N bonds. With excellent repeatability, stability, and specificity, the as-purposed sensing platform showed differentiated ECL responses of NSE range from 10.00 fg/mL to 500 ng/mL, and the limit of detection (LOD) was calculated of 6.30 fg/mL (S/N = 3). The proposed biosensor is prospective to provide a new avenue for the analysis of NSE or other biomarkers.


Asunto(s)
Técnicas Biosensibles , Puntos Cuánticos , Carbono/química , Puntos Cuánticos/química , Mediciones Luminiscentes/métodos , Nitrógeno/química , Molibdeno/química , Estudios Prospectivos , Técnicas Biosensibles/métodos , Inmunoensayo/métodos , Técnicas Electroquímicas/métodos , Límite de Detección
13.
Anal Chem ; 95(2): 1582-1588, 2023 01 17.
Artículo en Inglés | MEDLINE | ID: mdl-36596640

RESUMEN

Herein, a high-efficiency biosensor based on ternary electrochemiluminescence (ECL) system was constructed for procalcitonin (PCT) detection. Specifically, silver nanoclusters (Ag NCs) with stable luminescence properties were prepared with small-molecule lipoic acid (LA) as the ligand, and its ECL emission in persulfate (S2O82-) was first reported. Meanwhile, the prepared Ag NCs possessed ligand-to-metal charge-transfer characteristics, thus transferring energy from LA to Ag+ for luminescence. Based on the small particle size, good biocompatibility, and molecular binding ability, Ag NCs-LA was used as an ideal luminescent probe. In addition, α-Fe2O3-Pt was introduced to facilitate the activation of S2O82-, thereby generating more sulfate radicals to react with the free radicals of Ag NCs to enhance ECL emission. The synergistic effect of the variable valence state of transition metals and high catalytic activity of noble metals endows α-Fe2O3-Pt with excellent catalytic ability for S2O82-. Importantly, the sensing mechanism was systematically demonstrated by UV-vis, fluorescence, and ECL analysis, as well as density functional theory calculations. At last, NKFRGKYKC was designed for specific immobilization of antibodies, thus releasing the antigen binding sites to improve the antigen recognition efficiency. Based on this, the developed biosensor showed high sensitivity for PCT detection, with a wide linear range (10 fg/mL-100 ng/mL) and a low detection limit (3.56 fg/mL), which could be extended to clinical detection of multiple biomarkers.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Plata/química , Mediciones Luminiscentes , Polipéptido alfa Relacionado con Calcitonina/análisis , Ligandos , Inmunoensayo , Técnicas Electroquímicas , Nanopartículas del Metal/química , Límite de Detección
14.
Anal Chem ; 94(19): 7132-7139, 2022 05 17.
Artículo en Inglés | MEDLINE | ID: mdl-35522579

RESUMEN

The evolution of electrochemiluminescence (ECL) emission amplified by coreaction accelerator in near-infrared (NIR) area has been overwhelmingly anticipated for ultrasensitive detection of disease biomarkers. Herein, the hollow double-shell CuCo2O4@Cu2O (HDS-CuCo2O4@Cu2O) heterostructures were conveniently prepared and utilized as an attractive coreaction accelerator to improve the NIR ECL performance of gold nanoclusters (AuNCs) for the first time. Benefiting from perfect-matched lattice spacing, unique Cu2O nanoparticles (NPs) were formed in situ on the layered-hollow CuCo2O4 nanospheres (NSs) to obtain HDS-CuCo2O4@Cu2O heterostructures. The formed heterojunctions supplied shorter charge transfer distance and better interfacial charge transfer efficiency as well as more effective separation performance. Consequently, HDS-CuCo2O4@Cu2O heterostructures as an admirable electroactive substrate could significantly promote the formation of sufficient coreactant intermediate radicals to react with AuNCs cationic radicals, realizing about 3-folds stronger NIR ECL response than that of individual AuNCs. In addition, the AuNCs templated by l-methionine (l-Met) exhibited NIR ECL emission around 830 nm, which could decrease the photochemical damage to even realize a nondestructive detection with improved susceptibility and circumambient adaptability. Subsequently, a well site-oriented fixation strategy utilizing HWRGWVC heptapeptide as the specific antibody immobilizer was introduced to further preserve the bioactivity of antibody on the HDS-CuCo2O4@Cu2O and AuNCs surface along with enhancing the incubation performance markedly. In view of the progressive sensing mechanism, a NIR immunosensor was obtained for the ultrasensitive analysis of CYFRA21-1, which achieved a broad linear ranging from 2 fg/mL to 50 ng/mL and a low limit of detection (LOD) of 0.67 fg/mL (S/N = 3).


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Anticuerpos , Antígenos de Neoplasias , Técnicas Electroquímicas , Oro/química , Inmunoensayo , Queratina-19 , Límite de Detección , Mediciones Luminiscentes , Nanopartículas del Metal/química
15.
Carbohydr Polym ; 290: 119474, 2022 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-35550750

RESUMEN

Chiral recognition is of significant importance in the fields of chemical asymmetric synthesis and biological pharmaceutical research. In this work, an electrochemical chiral sensor with two kinds of chiral sites (chiral cavity for ß-cyclodextrin and chiral skeleton for Ca-sacc/MeOH) by electrooxidation ß-cyclodextrin onto Ca-sacc/MeOH was built. The proposed multichiral ß-CD@Ca-sacc/MeOH/GCE can be used for recognition of tryptophan and penicillamine enantiomers simultaneously with wide linear range, low detection limits value, high repeatability and stability within the available electrochemical window. The strategy for integration multichiral sources is crucial to construct novel chiral platforms for simultaneous recognition of multiple chiral compounds in complicated chiral systems.


Asunto(s)
Triptófano , beta-Ciclodextrinas , Técnicas Electroquímicas , Penicilamina , Estereoisomerismo , beta-Ciclodextrinas/química
16.
J Colloid Interface Sci ; 609: 414-422, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-34906913

RESUMEN

Highly efficient catalysts are required to solve the intrinsically sluggish kinetics of oxygen evolution reaction (OER). Herein, chromium doped cobalt carbonate hydroxide nanowire array on Ni foam (Cr-CoCH/NF) has been synthesized for the enhancement of OER activity and stability. Compared with pure CoCH/NF, Cr0.2-CoCH/NF, the optimal doping of Cr, shows a low overpotential of 203 mV at the current density of 10 mA cm-2 and a small Tafel slope of 84 mV dec-1 in 1.0 M NaOH. In addition, there is little deterioration in electrocatalytic performance after 1000-cycle cyclic voltammetry and the high activity can be maintained over 25 h. Density functional theory calculations reveal the Cr doping can regulate the electronic structure of nearby Co active center to achieve great enhancement of OER activity.

17.
Anal Chem ; 93(32): 11329-11336, 2021 08 17.
Artículo en Inglés | MEDLINE | ID: mdl-34342421

RESUMEN

A class of water-soluble electrochemiluminescence (ECL) nanodots were prepared by encapsulating ECL-active iridium complexes into biocompatible horse spleen apoferritin (apoHSF) nanocages for immunoassays. The preparation feasibility was achieved based on the pH-induced disassembly/reassembly nature originated from apoHSF. Two iridium nanodots (1 and 2) with high ECL efficiency were separately prepared by directing the self-assembly of two water-insoluble luminescent complexes, Ir(ppy)3 (ppy = 2-phenylpyridine) and Ir(ppy)2(acac) (ppy = 2-phenylpyridine and acac = acetylacetonate), in the apoHSF cavity. Using tri-n-propylamine (TPrA) as a coreactant, the electrochemistry and "oxidative-reductive" ECL mechanisms for nanodots 1 and 2 were investigated, respectively. After demonstrating the spectroscopic property and relative ECL efficiency, the ECL emission of nanodots 1 and 2 quenched by TPrA• radicals at high potential was further studied and circumvented by optimizing the potential range and TPrA concentration for generating strong and stable ECL emission in aqueous media. The well-inherited biological functions of apoHSF in nanodots allow the convenient external modification of an antibody to act as a signal probe, thus a versatile ECL immunoassay paradigm was established. Acceptable results from this assay enabled the rapid and accurate detection of biomarkers in real samples. The unprecedented use of apoHSF is feasible and applicable for water-insoluble iridium complexes to fabricate a wide variety of biocompatible ECL nanodots for potential bioanalysis.


Asunto(s)
Apoferritinas , Iridio , Animales , Técnicas Electroquímicas , Caballos , Inmunoensayo , Luminiscencia , Mediciones Luminiscentes
18.
Biosens Bioelectron ; 192: 113505, 2021 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-34298497

RESUMEN

Neuron-specific enolase (NSE) is the preferred marker for monitoring small cell lung cancer and neuroblastoma. We devised a dual-signal ratiometric electrochemiluminescence (ECL) sensing strategy for sensitive detection of NSE. In this work, Ru (bpy)32+ functionalized zinc-based metal-organic framework (Ru-MOF-5) nanoflowers (NFs) with plentiful carboxyl groups provide an excellent biocompatible sensing platform for the construction of immunosensor. Importantly, Ru-MOF-5 NFs possess stable and efficient "dual-potential" ECL emission of cathode (-1.5 V) and anode (1.5 V) in the existence of co-reactant K2S2O8. Simultaneously, the cathode ECL emitter ZnO-AgNPs are employed as the secondary antibody marker, whose participation amplify the cathode ECL signal as well attenuate the anode ECL emission of Ru-MOF-5 NFs. By monitoring the ECL dual-signal of -1.5 V and 1.5 V and calculating their ratios, a ratiometric strategy of quantified readout proportional is implemented for the proposed immunosensor to precise analyze NSE. Based on optimization conditions, the ECL immunosensor displays the wide linear range of 0.0001 ng/mL to 200 ng/mL and the minimum detection limit is 0.041 pg/mL. The "dual-potential" ratiometric ECL immunosensor effectively reduces system error or background signal by self-calibration from both emissions and improves detection reliability. The dual-signal ratiometric strategy with satisfactory reproducibility and stability provides further development possibilities for other biomolecular detection and analysis.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Estructuras Metalorgánicas , Técnicas Electroquímicas , Inmunoensayo , Límite de Detección , Mediciones Luminiscentes , Fosfopiruvato Hidratasa , Reproducibilidad de los Resultados , Zinc
19.
ACS Appl Mater Interfaces ; 13(24): 29179-29186, 2021 Jun 23.
Artículo en Inglés | MEDLINE | ID: mdl-34101420

RESUMEN

This research put forward a novel split-type electrochemical (EC) immunosensor which integrated the controlled-release strategy with EC detection for application in the field of biosensing. Concretely, ascorbic acid (AA) was packaged in a cadmium sulfide (CdS)-capped spherical mesoporous bioactive glass (SBG) nanocarrier (SBGCdS) on account of encapsulation technology. To reduce the complexity of the bioanalysis, the detection antibody-labeled SBGCdS-AA bioconjugate was applied in a 96-well microplate for the immunoreaction process, which is independent of the EC determination procedure. Thus, the immune interference and steric hindrance caused by the accumulation of nanomaterials on the electrode could be minimized. Subsequently, AA was released efficiently via the destruction effect of dithiothreitol on the disulfide bond. In addition, for the as-prepared FcAI/l-Cys/gold nanoparticles (GNPs)/porous BiVO4 (p-BVO)/ITO EC sensing platform in the detection solution, the synergetic catalysis of Fc and GNPs/p-BVO toward the oxidation of the released AA could be realized, which triggered AA-mediated significant signal magnification throughout this study. In particular, p-BVO with an ordered nanoarray structure could accelerate the electron transfer to assist in sensitivity improvement of this system. This novel biosensor was capable of assaying the neuron-specific enolase (NSE) biomarker sensitively, from which a linear range of 0.001-100 ng/mL was derived along with a low detection limit of 1.08 pg/mL. An innovative way could be paved in the bioanalysis of NSE and other biomarkers.


Asunto(s)
Ácido Ascórbico/química , Inmunoensayo/métodos , Nanopartículas del Metal/química , Fosfopiruvato Hidratasa/sangre , Anticuerpos Inmovilizados/inmunología , Biomarcadores/sangre , Técnicas Biosensibles/métodos , Bismuto/química , Compuestos de Cadmio/química , Técnicas Electroquímicas , Oro/química , Humanos , Límite de Detección , Fosfopiruvato Hidratasa/inmunología , Porosidad , Sulfuros/química , Vanadatos/química
20.
Anal Biochem ; 612: 114012, 2021 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-33189703

RESUMEN

A sandwich-type electrochemiluminescence (ECL) immunosensor based on the resonance energy transfer (RET) was proposed for ultrasensitive detection of cardiac troponin I (cTnI). The RET behavior could be generated between graphite carbon nitride nanosheets (m-CNNS) as donor and copper oxide@graphene oxide (CuO@GO) as acceptor, achieving the quenching effect of CuO@GO on m-CNNS for cTnI detection. The m-CNNS synthesized by mechanical grinding of the graphite carbon nitride (CN) not only has better dispersion and higher specific surface area, but also has high luminous efficiency and stable chemical properties. Therefore, m-CNNS was used as the matrix material and luminophore. As the acceptor, CuO@GO prepared by in-situ chemical synthesis of CuO NPs onto GO sheets also has a high specific surface area, which could be used as a label of secondary antibody (Ab2). Under optimal conditions, cTnI could be determined within the linear range of 0.1 pg mL-1 to 100 ng mL-1 and had a low detection limit (0.028 pg mL-1, S/N = 3). Meanwhile, the prepared ECL immunosensor possessed great stability, specificity and reproducibility, providing a new method for detecting cTnI and other biomarkers.


Asunto(s)
Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Transferencia Resonante de Energía de Fluorescencia/métodos , Fluoroinmunoensayo/métodos , Troponina I/análisis , Troponina I/sangre , Anticuerpos Inmovilizados/química , Cobre/química , Grafito/síntesis química , Grafito/química , Humanos , Límite de Detección , Nanoestructuras/química , Compuestos de Nitrógeno/química , Reproducibilidad de los Resultados
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